Support materials for three-dimensional printing

Abstract

The present disclosure relates generally to a support material for three-dimensional printing comprising a blend of at least two cellulose ethers or a blend of at least one cellulose ether and at least one vinyl pyrrolidone polymer. Additionally, the present disclosure relates to a shaped material and a three-dimensionally printed object comprising the support material. Furthermore, a process for producing a three-dimensional object using the support material is also disclosed.

What is claimed is: 
     
         1 . A support material for three-dimensional printing comprising: (i) a blend of at least one cellulose ether and at least one vinyl pyrrolidone polymer; or (ii) a blend of at least two cellulose ethers. 
     
     
         2 . The support material of  claim 1 , wherein the cellulose ether is selected from the group consisting of hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose and combinations thereof. 
     
     
         3 . The support material of  claim 2 , wherein the cellulose ether is hydroxypropyl cellulose or ethyl cellulose. 
     
     
         4 . The support material of  claim 3 , wherein the cellulose ether is hydroxypropyl cellulose having a weight average molecular weight in the range of from 2,000 to 2,000,000 Daltons. 
     
     
         5 . The support material of  claim 4 , wherein a molar substitution of the hydroxypropyl cellulose is from 2.0 to 5.0. 
     
     
         6 . The support material of  claim 3 , wherein the cellulose ether is ethyl cellulose having ethoxy contents in the range of from 35% to 60%. 
     
     
         7 . The support material of  claim 1 , wherein the vinyl pyrrolidone polymer is selected from the group consisting of a polyvinyl pyrrolidone (PVP), an alkylated polyvinyl pyrrolidone, a vinyl pyrrolidone/vinyl acetate (VP/VA) copolymer, a vinyl pyrrolidone/dimethylaminoethylmethacrylate (VP/DMAEMA) copolymer, a vinyl pyrrolidone/dimethylaminopropylmethacrylamide (VP/DMAPA) copolymer, a vinyl pyrrolidone/methacrylamidopropyl trimethylammonium chloride copolymer, a vinyl pyrrolidone/dimethylaminopropylmethacrylamide/methacrylamidopropyl trimethylammonium chloride terpolymer, a vinyl pyrrolidone/acrylic acid/lauryl methacrylate terpolymer, a vinyl pyrrolidone/acrylic acid copolymer, a vinyl pyrrolidone/vinyl caprolactam copolymer, a vinyl pyrrolidone/vinyl caprolactam/dimethylaminoethylmethacrylate terpolymer, a vinyl pyrrolidone/vinyl caprolactam/dimethylaminopropylmethacrylamide terpolymer, a vinyl pyrrolidone/vinyl caprolactam/dimethylaminopropylmethacrylamide/methacryloylaminopropyl lauryl dimethylammonium chloride tetrapolymer, and a vinyl pyrrolidone/styrene copolymer. 
     
     
         8 . The support material of  claim 7 , wherein a weight average molecular weight of the vinyl pyrrolidone polymer is from about 1,000 to about 3,000.000 Daltons. 
     
     
         9 . The support material of  claim 1 , wherein a ratio of the cellulose ether to the vinyl pyrrolidone polymer is from about 95:5 to about 5:95 by weight. 
     
     
         10 . The support material of  claim 1 , wherein the support material is present in a solid state of powder or granulate. 
     
     
         11 . A shaped material comprising the support material of  claim 1 . 
     
     
         12 . The shaped material of  claim 11 , wherein the shaped material has a shape of a pellet, a rod, or a filament. 
     
     
         13 . A three-dimensionally printed object comprising a build material and the support material of  claim 1 . 
     
     
         14 . The three-dimensionally printed object of  claim 13 , wherein the build material is selected from the group consisting of acrylonitrile butadiene styrene (ABS) copolymers, polylactic acid (PLA), polyamides, polyethylene, polypropylene, polycarbonates, polyoxymethylene (POM), ethylene vinyl acetate copolymers, polyphenylene ether, acrylonitrile styrene acrylate (ASA) copolymers, polyethylene terephthalate (PET), PETG (PET with a glycol modification), high impact polystyrene (HIPS), polyether ether ketone (PEEK), thermoplastic polyurethane, polyetherimide, and combinations thereof. 
     
     
         15 . Use of the support material of  claim 1  in three-dimensional printing. 
     
     
         16 . The use of  claim 15 , wherein the support material is used for supporting at least one layer of a build material. 
     
     
         17 . The use of  claim 16 , wherein the build material is selected from the group consisting of acrylonitrile butadiene styrene (ABS) copolymers, polylactic acid (PLA), polyamides, polyethylene, polypropylene, polycarbonates, polyoxymethylene (POM), ethylene vinyl acetate copolymers, polyphenylene ether, acrylonitrile styrene acrylate (ASA) copolymers, polyethylene terephthalate (PET), PETG (PET with a glycol modification), high impact polystyrene (HIPS), polyether ether ketone (PEEK), thermoplastic polyurethane, polyetherimide, and combinations thereof. 
     
     
         18 . The use of  claim 15 , wherein the three-dimensional printing comprises a fused deposition modeling. 
     
     
         19 . A process for producing a three-dimensional object comprising steps of:
 (i) depositing the support material of  claim 1  into a build chamber with a layer-based additive technique to form a support structure;   (ii) depositing a build material into the build chamber with the layer-based additive technique to form the three-dimensional object, wherein the three-dimensional object comprises at least one region supported by the support structure; and   (iii) removing the support structure from the three-dimensional object with a liquid medium.   
     
     
         20 . The process of  claim 19 , wherein the build material is selected from the group consisting of acrylonitrile butadiene styrene (ABS) copolymers, polylactic acid (PLA), polyamides, polyethylene, polypropylene, polycarbonates, polyoxymethylene (POM), ethylene vinyl acetate copolymers, polyphenylene ether, acrylonitrile styrene acrylate (ASA) copolymers, polyethylene terephthalate (PET), PETG (PET with a glycol modification), high impact polystyrene (HIPS), polyether ether ketone (PEEK), thermoplastic polyurethane, polyetherimide, and combinations thereof. 
     
     
         21 . The process of  claim 19 , wherein the liquid medium comprises water, an aqueous solution and a solvent. 
     
     
         22 . The process of  claim 21 , the liquid medium is the aqueous solution having a pH of about 5.0 to about 9.0.